CN112126236B - Porphyrin covalent organic framework/graphene aerogel composite material and electrochemical sensor and application thereof - Google Patents
Porphyrin covalent organic framework/graphene aerogel composite material and electrochemical sensor and application thereof Download PDFInfo
- Publication number
- CN112126236B CN112126236B CN202011088672.4A CN202011088672A CN112126236B CN 112126236 B CN112126236 B CN 112126236B CN 202011088672 A CN202011088672 A CN 202011088672A CN 112126236 B CN112126236 B CN 112126236B
- Authority
- CN
- China
- Prior art keywords
- nitric oxide
- cof
- organic framework
- covalent organic
- electrochemical sensor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明属于功能复合材料的制备和应用技术领域，提供一种卟啉共价有机骨架/石墨烯气凝胶复合材料及基于该复合材料的电化学传感器的制备方法和应用。由于卟啉共价有机骨架/石墨烯气凝胶复合材料具有3D多孔结构而展现出高的比表面积、高电导率和催化氧化的电化学活性，将其涂覆在玻碳电极上形成工作电极，用于构建一氧化氮电化学传感器，该传感器可以用于细胞释放一氧化氮的实时检测。该传感器在实际检测中展现出极低的检出限和高的选择性，而且其电化学性能稳定、循环使用寿命较长，便于商业化应用。The invention belongs to the technical field of preparation and application of functional composite materials, and provides a porphyrin covalent organic framework/graphene aerogel composite material and a preparation method and application of an electrochemical sensor based on the composite material. Since the porphyrin covalent organic framework/graphene aerogel composite exhibits high specific surface area, high electrical conductivity and electrochemical activity for catalytic oxidation due to its 3D porous structure, it was coated on glassy carbon electrode to form a working electrode , for the construction of a nitric oxide electrochemical sensor that can be used for real-time detection of nitric oxide released by cells. The sensor exhibits extremely low detection limit and high selectivity in actual detection, and its electrochemical performance is stable and the cycle life is long, which is convenient for commercial application.
Description
Technical Field
The invention relates to the technical field of preparation and application of functional composite materials, in particular to a porphyrin covalent organic framework/graphene aerogel composite material, an electrochemical sensor thereof and application of the porphyrin covalent organic framework/graphene aerogel composite material in detection of nitric oxide.
Background
Endogenous nitric oxide, as an important free radical messenger, plays an important role in many pathological and physiological processes, including nerve signaling, vasodilation, neurotransmission, blood pressure regulation, immune response, and the like. Nitric oxide is involved in regulating vital activities such as metabolism, proliferation, differentiation and apoptosis of cells under normal concentration, but when the concentration is too high, cytopathy can be caused, abnormal cell death can be caused, and body diseases can be caused, wherein pathological changes related to central nervous system, cardiovascular system, urogenital system, gastrointestinal tract activity, immune process and the like are usually abnormal along with the increase of nitric oxide concentration. Therefore, in situ real-time detection of nitric oxide released by cells is important for exploring its diverse roles in biological systems. However, real-time analysis of nitric oxide molecules present in complex biological systems remains a significant challenge due to their low concentration, fast diffusion, short half-life and susceptibility to oxidation. Methods for nitric oxide detection are numerous, including fluorescence, chemiluminescence, electrochemistry, and surface-enhanced raman spectroscopy. The electrochemical method has the advantages of fast reaction, easy miniaturization, long-term high calibration stability and high space-time resolution, so that the electrochemical sensor can be adopted to carry out real-time monitoring on the biomarker nitric oxide secreted by living cells.
Metalloporphyrins (MPor) have been widely used as excellent electrocatalysts for the electrochemical oxidation of many important analytes, which, based on their macrocyclic nature, include extended pi-pi systems, enabling them to undergo rapid redox. However, optimizing both the active sites and the conductivity remains a significant challenge for MPor-based electrochemical sensors. Covalent organic backbones (COFs), which are porous organic polymers, enable the fine integration of organic units into ordered structures with atomic precision by covalent bonds. The COF is prepared by taking MPor as a structural basic unit to form an ideal electrochemical sensor to enhance the electrocatalytic performance. However, most of the COFs have been reported to exist in the form of mesoporous or microporous microcrystalline powders, which greatly limits the use of COFs in diffusion processes and results in low catalytic activity. To overcome the challenges while maintaining precisely controllable active sites of atoms, Graphene Aerogels (GA) composed of a continuous three-dimensional interconnected network are used as scaffolds to grow or support electrocatalytic materials for various electrochemical applications. It can be seen from experiments and theories that the graphene-supported nitrogen coordinated metal atoms provide various active sites due to strong intermolecular interactions, while the graphene has a large specific surface area and efficient mass transport, provides a stable matrix for the metal atoms, and adjusts electron density. In addition, the three-dimensional GA macroporous channel network not only can effectively promote the transmission of electrons and the diffusion of electrolyte, but also provides an ideal three-dimensional matrix for the growth of living cells. Therefore, the combination of the good catalytic ability of COF and the macroporous channel network of GA can greatly improve the electrochemical catalytic ability, and an effective way is provided for developing a high-performance electrochemical sensor for detecting nitric oxide in real time.
Disclosure of Invention
The invention aims to provide a porphyrin covalent organic framework/graphene aerogel composite material for detecting nitric oxide, an electrochemical sensor and application thereof.
The invention adopts the following technical scheme:
a porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA) for detecting nitric oxide is characterized in that the preparation method is as follows:
(1) preparing graphene oxide into a 2-8mg/mL aqueous solution in a beaker, and taking out after freeze drying for 20-28 hours to obtain graphene oxide aerogel;
(2) reducing the graphene oxide aerogel by using 80% hydrazine hydrate solution at the temperature of 80-100 ℃ for 20-28 hours, and drying in vacuum for 20-28 hours to obtain reduced graphene oxide aerogel (GA);
(3) adding GA, 5,10,15, 20-tetra (4-aminophenyl) porphyrin iron Fe (TAPP), terephthalaldehyde, mesitylene, ethanol and acetic acid aqueous solution into a heat-resistant glass tube, carrying out ultrasonic treatment for 20-40 minutes, then carrying out three times of circular degassing treatment, sealing the tube, and heating the reaction at 110-130 ℃ for 70-74 hours; wherein the mass ratio of GA, 5,10,15, 20-tetra (4-aminophenyl) porphyrin iron Fe (TAPP) and terephthalaldehyde is 1:1.46:0.56, and the mass is 15.1-45.3 mg; the volume ratio of the mesitylene to the absolute ethyl alcohol to the acetic acid aqueous solution (6M) is 1:1:0.2, and the volume is 0.55-1.65 mL;
(4) after the reaction was complete, a dark purple precipitate was produced at the bottom of the tube and the product was obtained by centrifugation. And then, washing the solution with 1, 4-dioxane, tetrahydrofuran and acetone in sequence until the solution is colorless, and drying the solution at 70-80 ℃ for 12-14h to obtain purple black powder, thus obtaining the porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA).
Wherein the covalent organic skeleton is called COF-366-Fe for short, and the structural formula is shown as formula 1;
the application of the porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA) in the preparation of a nitric oxide electrochemical sensor.
An electrochemical sensor for detecting nitric oxide comprises a glassy carbon electrode and a porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA) coated on the glassy carbon electrode.
The preparation method of the electrochemical sensor for detecting nitric oxide comprises the following steps:
preparing a uniform suspension with the concentration of 4mg/mL from a porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA) by using ethanol, water and naphthol, coating 4-7 mu L of the suspension on a working electrode, and volatilizing a solvent to obtain an electrochemical sensor coated with the porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA) on the surface; wherein the volume ratio of the ethanol to the water to the naphthol is 1:0.3-0.5: 0.005-0.01.
The electrochemical sensor for measuring nitric oxide, which is prepared by the invention, adopts the material component of a novel composite material COF-366-Fe/GA constructed by a covalent organic framework (COF-366-Fe) and a reduced graphene oxide aerogel (GA), and the porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA) shows high specific surface area and electrochemical activity of catalytic oxidation, and is coated on an electrode to form a working electrode for constructing the nitric oxide electrochemical sensor, wherein the sensor shows excellent nitric oxide catalytic activity in the aspects of high sensitivity, linear range and quick response. In addition, it can be used to monitor nitric oxide secretion by isolated human umbilical vein endothelial cells.
The advantages of the invention are as follows:
(1) the preparation method of the porphyrin covalent organic framework/graphene aerogel composite material for detecting nitric oxide is simple, and the post-treatment is relatively easy;
(2) the electrochemical sensor for detecting nitric oxide has the advantages that nitric oxide can be effectively and rapidly detected, and potential safety hazards do not exist; detection of the linear range: 0.18-400 mu M, the detection limit is 30nM, the stability reaches the initial value of 90 percent after 20 days of continuous storage, the anti-interference performance is strong, the selectivity is good, and the method lays a foundation for the later application of the method in the detection of nitric oxide secreted by endothelial cells of human umbilical veins; the structure and the preparation process are simple, the cost is low, and industrialization is convenient to realize;
(3) the electrochemical sensor for detecting nitric oxide has the outstanding advantages of detecting the content of nitric oxide secreted by the endothelial cells of the human umbilical veins, can be widely applied to quickly capturing the gas messenger nitric oxide secreted by the endothelial cells of the human umbilical veins, and realizes the online and real-time monitoring of the nitric oxide secreted by the endothelial cells of the human umbilical veins.
Drawings
FIG. 1 is a scanning electron micrograph of COF-366-Fe/GA;
FIG. 2 is an elemental analysis diagram of COF-366-Fe/GA;
FIG. 3 is an IR map of COF-366-Fe/GA;
FIG. 4 is an X-ray diffraction pattern of COF-366-Fe/GA;
FIG. 5 is a graph of the size distribution of the mercury intrusion test for COF-366-Fe/GA;
FIG. 6 is XPS plot of COF-366-Fe/GA;
FIG. 7 shows a diagram of (A) a nitric oxide electrochemical sensor containing 5.0 mM [ Fe (CN)6] 3-/4-(ii) CV curve in 0.1M KCl, (B) corresponding linear relationship plot between peak current and square root of scan rate for oxidation and (C) reduction;
fig. 8 is a CV curve for different concentrations of nitric oxide in PBS solution (pH = 7.4) for an nitric oxide electrochemical sensor, inset: a linear plot of response versus different concentrations of nitric oxide;
FIG. 9 is a graph of (A) measured chronoamperometric response of a nitric oxide electrochemical sensor at 1.05V; (B) a linear plot of nitric oxide concentration versus current response;
FIG. 10 is a diagram (A) showing the results of the selectivity test of the nitric oxide electrochemical sensor on different interfering components and a corresponding selectivity map (B);
FIG. 11 is a nitric oxide electrochemical sensor stability;
FIG. 12 is a current curve of the nitric oxide electrochemical sensor under different conditions and (B) real-time detection of nitric oxide released from cells under different amounts of L-Arg stimulation;
FIG. 13 is a cytotoxicity test of nitric oxide electrochemical sensors on human umbilical vein endothelial cells.
Detailed Description
The invention is described in terms of specific embodiments, other advantages and benefits of the invention will become apparent to those skilled in the art from the description herein, and the invention may be practiced or applied to other embodiments and with various modifications and changes in detail without departing from the spirit of the invention.
It should be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween are optional unless the invention otherwise specified. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
The performance test of the invention adopts the following instruments: vertex70 IR spectrometer from Bruker, Germany, JEOL JSM-6700F scanning electron microscope from JEOL, D/max-gamma B X-ray diffractometer from Bruker, PoreMaster 60GT, CHI 760D electrochemical workstations.
The following further describes the embodiments of the present invention with reference to the drawings.
Example 1 preparation method of porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA)
1.1
(1) Preparing graphene oxide into a 5 mg/mL aqueous solution in a beaker, and taking out the graphene oxide after freeze drying for 24 hours to obtain graphene oxide aerogel;
(2) reducing the graphene oxide aerogel by using 80% hydrazine hydrate solution at 90 ℃ for 24 hours, and drying in vacuum for 24 hours to obtain reduced graphene oxide aerogel (GA);
(3) GA (10 mg), 5,10,15, 20-tetra (4-aminophenyl) iron porphyrin (Fe) (TAPP) (14.6 mg), terephthalaldehyde (5.6 mg), mesitylene (0.5 mL), ethanol (0.5 mL) and an aqueous solution of acetic acid (6M, 0.1 mL) were added to a heat-resistant glass tube, subjected to ultrasonic treatment for 30 minutes, subjected to degassing treatment for three cycles, sealed, and the reaction was heated at 120 ℃ for 72 hours;
(4) after the reaction was complete, a dark purple precipitate was produced at the bottom of the tube and the product was obtained by centrifugation. Then, washing the materials by using 1, 4-dioxane, tetrahydrofuran and acetone in sequence until the materials are colorless, and drying the materials at 70 ℃ for 12 hours to obtain purple black powder, thus obtaining the porphyrin covalent organic framework/graphene aerogel composite material COF-366-Fe/GA;
(5) comprehensively characterizing the obtained product, observing the appearance of the product by using a scanning electron microscope, wherein the appearance of the product is a 3D porous frame which is connected with each other and is formed by a folded sheet with continuous macropores, and clearly showing that COF-366-Fe microcrystals are uniformly dispersed and embedded into a GA layer in an enlarged view; the element analysis chart shows that the COF-366-Fe/GA contains C, N, O, Fe four elements, which proves that the COF-366-Fe and the GA are compounded together; the synthesis of COF-366-Fe/GA was confirmed by infrared and X-ray diffraction; the pore diameter of COF-366-Fe/GA obtained by mercury intrusion test is about 13.7 mu m, and the BET surface area is 230.0 m2Per g, it can be shown that COF-366-Fe/GA has a high surface area; XPS confirmed that COF-366-Fe was successfully attached to the GA surface
1.2
(1) Preparing graphene oxide into a 2 mg/mL aqueous solution in a beaker, and taking out the graphene oxide after freeze drying for 20 hours to obtain graphene oxide aerogel;
(2) reducing the graphene oxide aerogel by using 80% hydrazine hydrate solution at 80 ℃ for 20 hours, and drying in vacuum for 20 hours to obtain reduced graphene oxide aerogel (GA);
(3) GA (5 mg), 5,10,15, 20-tetra (4-aminophenyl) iron porphyrin Fe (TAPP) (7.3 mg), terephthalaldehyde (2.8 mg), mesitylene (0.25 mL), ethanol (0.25 mL) and an aqueous solution of acetic acid (6M, 0.05 mL) were added to a heat-resistant glass tube, subjected to ultrasonic treatment for 20 minutes, subjected to degassing treatment for three cycles, sealed, and the reaction was heated at 110 ℃ for 70 hours;
(4) after the reaction was complete, a dark purple precipitate was produced at the bottom of the tube and the product was obtained by centrifugation. Then, washing the solution with 1, 4-dioxane, tetrahydrofuran and acetone in sequence until the solution is colorless, and drying the solution at 75 ℃ for 13 hours to obtain purple black powder, thus obtaining the porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA);
(5) the solid product obtained was fully characterized: the results were in accordance with 1.1
1.3
(1) Preparing graphene oxide into an 8mg/mL aqueous solution in a beaker, and taking out after freeze drying for 28 hours to obtain graphene oxide aerogel;
(2) reducing the graphene oxide aerogel by using 80% hydrazine hydrate solution at 100 ℃ for 28 hours, and performing vacuum drying for 28 hours to obtain reduced graphene oxide aerogel (GA);
(3) GA (15 mg), 5,10,15, 20-tetra (4-aminophenyl) iron porphyrin (Fe) (TAPP) (21.9 mg), terephthalaldehyde (8.4 mg), mesitylene (0.75 mL), ethanol (0.75 mL) and an aqueous solution of acetic acid (6M, 0.15 mL) were added to a heat-resistant glass tube, subjected to ultrasonic treatment for 40 minutes, then subjected to degassing treatment for three cycles, sealed, and the reaction was heated at 130 ℃ for 74 hours;
(4) after the reaction was complete, a dark purple precipitate was produced at the bottom of the tube and the product was obtained by centrifugation. Then, washing the solution with 1, 4-dioxane, tetrahydrofuran and acetone in sequence until the solution is colorless, and drying the solution at 80 ℃ for 14 hours to obtain purple black powder, thus obtaining the porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA);
(5) the solid product obtained was fully characterized: the results were in agreement with 1.1.
EXAMPLE 2 preparation of nitric oxide electrochemical sensor
2.1
2 mg of porphyrin covalent organic framework/graphene aerogel composite material COF-366-Fe/GA is uniformly dispersed in 375 mu L of ethanol and 125 mu L of deionized water solvent containing 2 mu L of naphthol (5 wt%). Then, 5 μ L of the prepared mixture is coated on a pretreated glassy carbon electrode and dried at room temperature overnight to obtain the nitric oxide electrochemical sensor
2.2
4mg of porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA) is uniformly dispersed in 750 muL of ethanol and 250 muL of deionized water solvent containing 4 muL of naphthol (5 wt%). Subsequently, 7 μ L of the prepared mixture was applied to a pretreated glassy carbon electrode and dried overnight at room temperature to obtain a nitric oxide electrochemical sensor.
EXAMPLE 3 Performance measurement of nitric oxide electrochemical sensor
Adopting a three-electrode system, taking the glassy carbon electrode coated with the COF-366-Fe/GA composite material on the surface and prepared in the example 2 as a working electrode, a platinum wire as a counter electrode, a saturated calomel electrode as a reference electrode, and an electrolyte solution of 0.01M PBS (pH 7.4), and meanwhile preparing a PBS (1.8 mM) solution containing saturated nitric oxide, and detecting the performance of the glassy carbon electrode by using an electrochemical workstation through various methods;
the CV curve of a COF-366-Fe/GA modified glassy carbon electrode is tested in nitric oxide solutions with different concentrations by adopting a cyclic voltammetry method, the scanning rate is set to be 0.1V/s, the scanning range is 0-1.2V, the experimental result is shown in figure 8, and the result shows that in the concentration range of 0-432 mu M, the response current is gradually increased along with the increase of the concentration, the nitric oxide concentration and the current response form a linear relation, and the oxidation peak of nitric oxide appears at 1.05V;
by utilizing a timing current method, applying 1.05V of potential, continuously adding nitric oxide solutions with different concentrations into an electrolyte during testing, wherein the time interval is 50 s, recording a relation curve of response time and current value to obtain an i-t diagram of the sensor to nitric oxide, and as a result, as shown in fig. 9, after adding nitric oxide with different concentrations, the current response of the sensor is continuously increased and reaches a steady state within a relatively fast time, the response time is less than 3s, the reproducibility is good, meanwhile, a good relation exists between the nitric oxide concentration and the current response, the linear response range is 0.18-400 mu M, and the detection limit is 30 nM;
in addition, a timing current method is adopted for anti-interference experiments, solutions of different substances of 36 mu M are sequentially added into the electrolyte, the result is shown in fig. 10, the result shows that the response current is almost unchanged when anti-interference ions are added, and the current is rapidly increased when the nitric oxide solution is added, so that the sensor has good anti-interference capability and selectivity;
the response of the sensor placed for different days to nitric oxide is tested under the voltage range of 0-1.2V by adopting a cyclic voltammetry, the same sensor is used during testing, the concentration of nitric oxide added every time is kept unchanged after the test is carried out every 5 days, the test is carried out for 5 times, and the result is shown in figure 11, which shows that the stability of the sensor in 20 days is basically consistent, and the stability of the sensor is good;
by adopting cyclic voltammetry, an electrolytic cell is a culture dish for culturing cells, a PBS solution with the concentration of 0.01M and the pH value of 7.4 is used as an electrolyte, CV curves of nitric oxide released by the cells under the stimulation of L-Arg and L-Name medicines are tested, and simultaneously, the cells release nitric oxide under the stimulation of different concentrations of L-Arg medicines are tested, and the result is shown in figure 12, and it can be seen that the sensor can detect the nitric oxide released by the cells in real time, and at low dose of L-Arg, the nitric oxide released by the cells depends on the medicine concentration, however, the peak current intensity is not completely proportional to the higher dose of L-Arg, which is probably attributed to the complex biosynthesis process of the nitric oxide in the living cells;
the MTT method (3- (4, 5-dimethylthiazol-2-yl) -2, 5-diphenyltetrazolium ammonium bromide) was used to test the cytotoxicity of COF-366-Fe/GA on human umbilical vein endothelial cells. As shown in FIG. 13, after 24 hours of incubation with high concentration of COF-366-Fe/GA (2 mg/mL), the survival rate of human umbilical vein endothelial cells remained above 80%, indicating that COF-366-Fe/GA has low toxicity to living cells and good biocompatibility.
In conclusion, the porphyrin covalent organic framework/graphene aerogel composite material (COF-366-Fe/GA) electrochemical sensor has the advantages of quick response, high sensitivity, good selectivity and excellent stability when being used for measuring nitric oxide. In addition, the sensor can be flexibly used for identifying nitric oxide secreted by a complex biological system in real time. This makes the method universally applicable in real life and industrial production.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011088672.4A CN112126236B (en) | 2020-10-13 | 2020-10-13 | Porphyrin covalent organic framework/graphene aerogel composite material and electrochemical sensor and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011088672.4A CN112126236B (en) | 2020-10-13 | 2020-10-13 | Porphyrin covalent organic framework/graphene aerogel composite material and electrochemical sensor and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112126236A CN112126236A (en) | 2020-12-25 |
| CN112126236B true CN112126236B (en) | 2022-03-25 |
Family
ID=73853638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011088672.4A Active CN112126236B (en) | 2020-10-13 | 2020-10-13 | Porphyrin covalent organic framework/graphene aerogel composite material and electrochemical sensor and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112126236B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854214B (en) * | 2021-02-03 | 2023-03-31 | 中国科学院化学研究所 | In-situ growth graphene two-dimensional covalent organic framework composite material and preparation method thereof |
| CN114113265B (en) * | 2021-12-14 | 2023-08-08 | 郑州轻工业大学 | Aptamer sensor and preparation method thereof |
| CN114591475A (en) * | 2022-03-11 | 2022-06-07 | 济南大学 | A kind of covalent organic framework/graphene composite material and its preparation method and application |
| CN114685802A (en) * | 2022-03-31 | 2022-07-01 | 国家纳米科学中心 | Silicon-based covalent organic framework photoelectrode and preparation method and application thereof |
| CN114878663B (en) * | 2022-06-24 | 2023-10-13 | 济南大学 | A bimetallic covalent organic framework material and its electrochemiluminescence sensor and application |
| CN115612376B (en) * | 2022-11-12 | 2023-09-05 | 广东百川化工有限公司 | Preparation method of water-based paint |
| CN118557784B (en) * | 2024-08-01 | 2024-10-15 | 山东第二医科大学 | Graphene oxide-based calcium phosphate composite material and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112011103068T5 (en) * | 2010-09-13 | 2013-08-22 | Cornell University | Films of a covalent organic framework and process for their preparation and their use |
| KR101669169B1 (en) * | 2014-12-19 | 2016-10-26 | 한국생산기술연구원 | Composites of carbon materials and covalent-organic frameworks, a preparation method thereof and a use thereof |
| CN106882797A (en) * | 2017-01-15 | 2017-06-23 | 复旦大学 | A kind of grapheme material of covalent organic frame modification and its synthetic method and application |
| CN107970894A (en) * | 2017-12-11 | 2018-05-01 | 哈尔滨理工大学 | A kind of preparation method and application of COF/GO adsorbents |
| CN109959681A (en) * | 2017-12-22 | 2019-07-02 | 中国科学院物理研究所 | A kind of gas sensor device and its preparation method and application |
| CN109148165B (en) * | 2018-08-01 | 2020-10-13 | 曲阜师范大学 | Preparation and application of covalent organic framework/graphene composite material |
| CN109524652B (en) * | 2018-11-16 | 2020-06-30 | 华南师范大学 | A kind of covalent organic framework/graphene composite organic material and preparation method and application in lithium/sodium ion battery negative electrode material |
-
2020
- 2020-10-13 CN CN202011088672.4A patent/CN112126236B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112126236A (en) | 2020-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112126236B (en) | Porphyrin covalent organic framework/graphene aerogel composite material and electrochemical sensor and application thereof | |
| Guan et al. | Electrochemical sensor based on covalent organic frameworks-MWCNT-NH2/AuNPs for simultaneous detection of dopamine and uric acid | |
| Arul et al. | Silver nanoparticles built-in zinc metal organic framework modified electrode for the selective non-enzymatic determination of H2O2 | |
| Qiu et al. | An electrochemical ratiometric sensor based on 2D MOF nanosheet/Au/polyxanthurenic acid composite for detection of dopamine | |
| Fang et al. | Black phosphorus quantum dots functionalized MXenes as the enhanced dual-mode probe for exosomes sensing | |
| Qu et al. | Designing C-Fe-O bonded MIL-88B (Fe)/jasmine petal-derived-carbon composite biosensor for the simultaneous detection of dopamine and uric acid | |
| Wang et al. | A novel triazine-based covalent organic framework combined with AuNPs and reduced graphene oxide as an electrochemical sensing platform for the simultaneous detection of uric acid, dopamine and ascorbic acid | |
| Dai et al. | High-performance electrochemical biosensor for nonenzymatic H2O2 sensing based on Au@ C-Co3O4 heterostructures | |
| Zhu et al. | Hierarchical flower-like zinc oxide nanosheets in-situ growth on three-dimensional ferrocene-functionalized graphene framework for sensitive determination of epinephrine and its oxidation derivative | |
| Wang et al. | A novel ratiometric electrochemical biosensor for sensitive detection of ascorbic acid | |
| Zhuang et al. | Manganese dioxide nanosheet-decorated ionic liquid-functionalized graphene for electrochemical theophylline biosensing | |
| Chen et al. | Integrating polythiophene derivates to PCN-222 (Fe) for electrocatalytic sensing of L-dopa | |
| Ensafi et al. | Characterization of MgFe2O4 nanoparticles as a novel electrochemical sensor: application for the voltammetric determination of ciprofloxacin | |
| Lopa et al. | A chemically and electrochemically stable, redox-active and highly sensitive metal azolate framework for non-enzymatic electrochemical detection of glucose | |
| Ma et al. | Electrocatalysis and simultaneous determination of hydroquinone and acetaminophen using PNCOF/graphene oxide modified electrode | |
| Tian et al. | Amperometric detection of glucose based on immobilizing glucose oxidase on g-C3N4 nanosheets | |
| CN109507272A (en) | A kind of NiCoLDH@Au composite material based on ZIF-67 synthesis and its application in glucose sensor | |
| CN108982622A (en) | Electrochemical sensor and preparation method thereof based on the vertical graphene composite structure of metal organic frame- | |
| Su et al. | Covalent organic frameworks and electron mediator-based open circuit potential biosensor for in vivo electrochemical measurements | |
| CN112110439A (en) | Preparation method and application of carbon nanotube-wrapped nitrogen-doped porous carbon composite material | |
| CN102944598A (en) | Preparation method and application of cell based sensor based on electrochemical reduction graphite oxide/gold nanoparticle composite membrane | |
| Usman et al. | Ultra-fast and highly sensitive enzyme-free glucose sensor based on 3D vertically aligned silver nanoplates on nickel foam-graphene substrate | |
| Sakthinathan et al. | Reduced graphene oxide/gold tetraphenyl porphyrin (RGO/Au–TPP) nanocomposite as an ultrasensitive amperometric sensor for environmentally toxic hydrazine | |
| Singh et al. | Palladium nanoparticles decorated electrostatically functionalized MWCNTs as a non enzymatic glucose sensor | |
| CN106525933A (en) | Method for producing polypyrrole-coated nickel cobaltate nano wire array graphene electrode and application of graphene electrode for detecting heavy metallic lead ion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |